CN109487198B - Preparation method of rare earth metal-molybdenum binary infiltration layer for kovar alloy surface - Google Patents
Preparation method of rare earth metal-molybdenum binary infiltration layer for kovar alloy surface Download PDFInfo
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- CN109487198B CN109487198B CN201811562229.9A CN201811562229A CN109487198B CN 109487198 B CN109487198 B CN 109487198B CN 201811562229 A CN201811562229 A CN 201811562229A CN 109487198 B CN109487198 B CN 109487198B
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 83
- 239000000956 alloy Substances 0.000 title claims abstract description 83
- 229910000833 kovar Inorganic materials 0.000 title claims abstract description 74
- 230000008595 infiltration Effects 0.000 title claims abstract description 61
- 238000001764 infiltration Methods 0.000 title claims abstract description 61
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 54
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 54
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 39
- 239000011733 molybdenum Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 54
- 238000007750 plasma spraying Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 21
- 238000012360 testing method Methods 0.000 claims abstract description 9
- 238000007747 plating Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims description 46
- 238000000576 coating method Methods 0.000 claims description 46
- 239000011159 matrix material Substances 0.000 claims description 32
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000005507 spraying Methods 0.000 claims description 22
- 238000005488 sandblasting Methods 0.000 claims description 15
- 239000001294 propane Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 229910052772 Samarium Inorganic materials 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 6
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000010431 corundum Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000004519 grease Substances 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 229910001369 Brass Inorganic materials 0.000 claims description 3
- 229910000906 Bronze Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 3
- 239000010951 brass Substances 0.000 claims description 3
- 239000010974 bronze Substances 0.000 claims description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 3
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 2
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims 6
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 2
- 238000009863 impact test Methods 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 238000005238 degreasing Methods 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 description 15
- 230000003213 activating effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
Abstract
The invention provides a preparation method of rare earth metal-molybdenum binary infiltration layer for kovar alloy surface, which comprises the following steps: and forming a uniform and compact rare earth metal-molybdenum binary infiltration layer on the surface of the kovar alloy by adopting a supersonic plasma spraying technology. And (3) carrying out combined degreasing and acid washing activation on the kovar alloy, and adopting a supersonic plasma spraying method to prepare a rare earth metal-molybdenum binary infiltration layer and a post-treatment procedure of infiltration. The obtained kovar alloy rare earth metal-molybdenum binary infiltration layer has good binding force and fine and smooth appearance, can withstand atomic oxygen impact test and high and low temperature impact test in a low-orbit space environment, and meets the requirements of comprehensive performances such as tensile strength and the like. Experiments and tests demonstrate the feasibility of the process. The rare earth metal-molybdenum binary infiltration layer is prepared on the surface of the kovar alloy by adopting a supersonic plasma spraying technology, and the method has the technical advantages of simple process, low cost, zero pollution, obvious comprehensive effect of the plating layer and the like.
Description
Technical Field
The invention belongs to the field of kovar alloy, relates to a binary infiltration layer, and in particular relates to a preparation method of a rare earth metal-molybdenum binary infiltration layer for the surface of the kovar alloy.
Background
The kovar alloy, the hard glass iron-based sealing alloy containing 29% of nickel and 17% of cobalt, has good structure stability, conductivity, welding performance and welding performance. The alloy has the linear expansion coefficient similar to that of hard glass in the range of 20-450 ℃ and can be effectively sealed and matched with the corresponding hard glass, in addition, the Curie point is higher, the low-temperature tissue stability is good, the oxide film of the alloy is compact, the welding and the welding are easy, the plasticity is good, the cutting processing and other excellent characteristics are realized, and the alloy is widely used for manufacturing electric vacuum elements, transmitting tubes, kinescope, switching tubes, transistors, sealing plugs, relay shells and the like. In order to further optimize the performance of kovar alloys, there are reports in foreign literature of the electroplating treatment on kovar alloy foils. The invention provides a method for preparing a uniform and compact rare earth metal-molybdenum binary infiltration layer on the surface of a kovar alloy by adopting a supersonic plasma spraying technology, wherein rare earth metal is used as an infiltration activating agent in an infiltration layer system, a certain amount of molybdenum powder particles can improve the dispersion capacity of the infiltration layer system, the preferred orientation and texture coefficient of crystal faces of the kovar alloy infiltration layer are changed, the crystal grains of the plating layer are thinned, a uniform and compact plating layer is obtained, and the technical advantages of simple process, low cost, zero pollution, obvious plating effect and the like are realized.
The supersonic plasma spraying (SAPS) is one kind of hot spraying technology developed successfully in 90 s of 20 th century, and features high flame flow temperature and fast particle flying speed, and in the central area of plasma arc, the temperature may reach 32000K and the particle flying speed may reach 400-800 m/s. Compared with the supersonic flame spraying technology and the traditional subsonic plasma spraying technology, the SAPS can prepare a coating with higher quality due to low cost and high efficiency; the working gas of the SAPS is compressed air and low-flow propane or methane (1-2 m 3/H), and expensive gas (Ar (or N2) +H2) is not needed; the speed and temperature of the supersonic plasma arc ensure the spraying efficiency (reaching more than 20-25 kg/h) of the high-melting-point material coating. The rare earth metal-molybdenum diffusion coating prepared by supersonic plasma spraying has high tissue density and high interface bonding strength. The invention adopts the supersonic plasma spraying technology, improves the density of the infiltration layer, reduces the internal defects of the infiltration layer, reduces the residual stress of the infiltration layer in the heating process, ensures that the coating performance is excellent, the infiltration layer structure is more compact, and the performance is more excellent.
At present, a kovar alloy plating piece with a gold plating layer is usually prepared by adopting an electroplating method, and the method relates to the electroplating method, and has high cost and great pollution, so that the development of a preparation method for the rare earth metal-molybdenum binary infiltration layer on the surface of the kovar alloy has positive significance.
Disclosure of Invention
Based on the problems existing in the prior art, the invention provides a preparation method of a rare earth metal-molybdenum binary infiltration layer for the surface of a kovar alloy, which solves the technical problems of low binary infiltration rate, poor comprehensive performance of the kovar alloy caused by thin infiltration layer thickness and the like in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme: the preparation method of the rare earth metal-molybdenum binary infiltration layer for the surface of the kovar alloy is characterized by comprising the following steps of:
the technical problem to be solved by the invention is to solve the defects in the prior art, namely a preparation method of rare earth metal-molybdenum binary infiltration layer for the surface of kovar alloy. The method adopts a supersonic plasma spraying technology, adopts kovar alloy as a matrix material and adopts rare earth metal-molybdenum binary alloy as a diffusion coating to obtain optimal technological parameters, including the doping amount of rare earth metal, the spray current of supersonic plasma spraying, air pressure, the spray distance and other parameters, so as to realize the preparation of the diffusion coating with good and stable comprehensive performance.
In order to solve the technical problems, the application is realized by adopting the following technical scheme:
step one, preprocessing a kovar alloy matrix: thoroughly removing greasy dirt, residues and oxide films on the surface of a matrix to obtain a clean active surface, and placing the kovar alloy matrix in alcohol for ultrasonic cleaning for 15min to remove surface grease; treating the surface of the kovar alloy matrix by using a sand blasting machine, and performing sand blasting coarsening treatment by using 46# brown corundum, wherein the sand blasting pressure is 0.4MPa; and taking out, washing with deionized water and alcohol, and drying to obtain the kovar alloy matrix.
Step two, preparing rare earth metal-molybdenum binary infiltration layer: rare earth metals are used as permeation activators in a permeation coating system, and lanthanum (La), cerium (Ce), neodymium (Nd) or samarium (Sm) are respectively selected. According to the invention, rare earth La is taken as an example, the influence of La elements with different contents on the comprehensive performance of the diffusion coating is examined, wherein the selected range of La element content is 1.0-3.0%; and a certain amount of molybdenum powder particles improve the dispersion capacity of a coating permeation system, change the preferred orientation and texture coefficient of crystal faces of the kovar alloy coating permeation layer, refine the crystal grains of the coating and obtain a uniform and compact coating.
And thirdly, comparing the spraying process, selecting the optimal technological parameters of the supersonic plasma spraying technology, and forming a uniform and compact rare earth metal-molybdenum binary infiltration layer on the surface of the kovar alloy.
And step four, testing the thickness and the binding force of the infiltration layer.
A process for preparing rare-earth metal-Mo binary coating on the surface of kovar alloy features that ultrasonic plasma spraying technique is used to research the binary coating technique of kovar alloy by using rare-earth metal as the activating agent.
The supersonic plasma spraying process is characterized in that propane and compressed air are used as plasma forming gas, and the ratio of the compressed air amount to the propane amount is 5:1. The spraying current is 270-350A; the air pressure is 0.4-0.6 MPa; the spraying distance is 170-230 mm.
The rare earth metal of the catalytic permeation activator is lanthanum (La), cerium (Ce), neodymium (Nd) or samarium (Sm).
The kovar alloy matrix is made of 4J29, and is suitable for stainless steel (chrome alloy-containing steel), copper and copper alloy (brass and bronze), iron-nickel alloy and iron-nickel-chromium alloy systems for glass sealing.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts supersonic plasma spraying technology, adopts kovar alloy as matrix material, rare earth metal-molybdenum binary alloy as a diffusion coating, obtains proper technological parameters, realizes the diffusion coating preparation with good and stable comprehensive performance, has the technical advantages of simple process, low cost, zero pollution, obvious comprehensive effect of the coating and the like, provides a new thought for preparing the kovar alloy coating, and also avoids environmental problems caused by adopting a plating system.
2. The kovar alloy with the binary infiltration layer prepared by the method has better matching and sealing effect with glass, and can resist oxidation corrosion at the use temperature; the La-Mo binary infiltration layer prepared by the method has good compatibility with the kovar alloy matrix, and is not easy to crack and fall off. The kovar alloy treated by the surface binary infiltration layer has good sealing property, temperature uniformity and structural stability.
3. The rare earth La prepared by the method can increase the diffusion coefficient of molybdenum, reduce the diffusion activation energy, obviously improve the molybdenum permeation rate and greatly improve the industrial production efficiency.
4. The molybdenum powder particles prepared by the method of the invention improve the dispersion capacity of a coating permeation system, change the preferred orientation and texture coefficient of crystal faces of the kovar alloy coating permeation, refine the crystal grains of the coating and obtain a uniform and compact coating.
5. The thickness of the La-Mo binary diffusion coating prepared by the method is increased from 5 mu m of the diffusion coating thickness without adding the permeation activating agent to 10 mu m of the diffusion coating thickness, so that the thickness of the La-Mo binary diffusion coating is increased by 2 times, and the comprehensive performance of the kovar alloy at the use temperature is improved.
6. The kovar alloy with the binary infiltration layer prepared by the method is simple to operate, and does not need complex infiltration technology and equipment.
Detailed Description
Example 1
The method of the present embodiment includes the steps of:
step one, preprocessing a kovar alloy matrix: the greasy dirt, residue and oxide film on the surface of the substrate need to be thoroughly removed to obtain a clean active surface. Placing the kovar alloy matrix in alcohol for ultrasonic cleaning for 15min to remove surface grease; treating the surface of the kovar alloy matrix by using a sand blasting machine, and performing sand blasting coarsening treatment by using 46# brown corundum, wherein the sand blasting pressure is 0.4MPa; and taking out, washing with deionized water and alcohol, and drying to obtain the kovar alloy matrix.
Step two, preparing rare earth metal-molybdenum binary infiltration layer: rare earth metals are used as permeation activators in a permeation coating system, and lanthanum (La), cerium (Ce), neodymium (Nd) or samarium (Sm) are respectively selected. And are not given in one-to-one fashion for reasons of space. Lanthanum (La) is used as a representative, and the influence of La elements with different contents on the comprehensive performance of the diffusion coating is examined. Wherein the selected range of La element content is 1.0%.
Thirdly, forming a uniform and compact rare earth metal-molybdenum binary infiltration layer on the surface of the kovar alloy by adopting a supersonic plasma spraying technology: the supersonic plasma spraying process is characterized in that propane and compressed air are used as plasma forming gas, and the ratio of the compressed air amount to the propane amount is 5:1. The spraying current is 270A; the air pressure is 0.4MPa; the spray distance was 170mm.
And step four, testing the thickness and the binding force of the infiltration layer. The experiment tests the bonding strength between the coating and the substrate according to the scratch method: the bonding strength of the infiltration layer and the kovar alloy matrix is measured by a scratch method, the thickness of the coating is 8 mu m, the bonding property with the matrix is good, and the microhardness is 2500HV0.2.
Comparative examples 1 to 1
The specific process of the preparation method for the rare earth metal-molybdenum binary infiltration layer on the surface of the kovar alloy is the same as that of the embodiment 1, and specific technological parameter conditions are shown in the table 1, wherein the difference is that the spraying distance selected by adopting a supersonic plasma spraying technology in the embodiment is 200mm.
Comparative examples 1 to 2
The specific process of the preparation method for the rare earth metal-molybdenum binary infiltration layer on the surface of the kovar alloy is the same as that of the embodiment 1, and specific technological parameter conditions are shown in the table 1, wherein the difference is that the spraying distance selected by adopting a supersonic plasma spraying technology in the embodiment is 230mm.
Example 2
The method of the present embodiment includes the steps of:
step one, oil stains, residues and oxide films on the surface of a substrate need to be thoroughly removed, and a clean active surface is obtained. Placing the kovar alloy matrix in alcohol for ultrasonic cleaning for 15min to remove surface grease; treating the surface of the kovar alloy matrix by using a sand blasting machine, and performing sand blasting coarsening treatment by using 46# brown corundum, wherein the sand blasting pressure is 0.4MPa; and taking out, washing with deionized water and alcohol, and drying to obtain the kovar alloy matrix.
Step two, preparing rare earth metal-molybdenum binary infiltration layer: rare earth metals are used as permeation activators in a permeation coating system, and lanthanum (La), cerium (Ce), neodymium (Nd) or samarium (Sm) are respectively selected. The invention takes rare earth La as an example to examine the influence of La elements with different contents on the comprehensive performance of the diffusion coating. Wherein the selected range of La element content is 2.0%.
Thirdly, forming a uniform and compact rare earth metal-molybdenum binary infiltration layer on the surface of the kovar alloy by adopting a supersonic plasma spraying technology: the supersonic plasma spraying process is characterized in that propane and compressed air are used as plasma forming gas, and the ratio of the compressed air amount to the propane amount is 5:1. The spraying current is 310A; the air pressure is 0.5MPa; the spraying distance was 200mm.
And step four, testing the thickness and the binding force of the infiltration layer. The experiment tests the bonding strength between the coating and the substrate according to the scratch method: the bonding strength of the infiltration layer and the kovar alloy matrix is measured by a scratch method, the thickness of the coating is 10 mu m, the bonding property with the matrix is good, and the microhardness is 3000HV0.4.
Comparative example 2-1
The embodiment provides a preparation method of rare earth metal-molybdenum binary infiltration layer for the surface of kovar alloy, the specific process is the same as that of embodiment 1, and specific technological parameter conditions are shown in table 1, except that the air pressure selected by adopting the supersonic plasma spraying technology in the embodiment is 0.4MPa.
Comparative examples 2 to 2
The embodiment provides a preparation method of rare earth metal-molybdenum binary infiltration layer for the surface of kovar alloy, the specific process is the same as that of embodiment 1, and specific technological parameter conditions are shown in table 1, except that the air pressure selected by adopting the supersonic plasma spraying technology in the embodiment is 0.6MPa.
Example 3
The method of the present embodiment includes the steps of:
step one, oil stains, residues and oxide films on the surface of a substrate need to be thoroughly removed, and a clean active surface is obtained. Placing the kovar alloy matrix in alcohol for ultrasonic cleaning for 15min to remove surface grease; treating the surface of the kovar alloy matrix by using a sand blasting machine, and performing sand blasting coarsening treatment by using 46# brown corundum, wherein the sand blasting pressure is 0.4MPa; and taking out, washing with deionized water and alcohol, and drying to obtain the kovar alloy matrix.
Step two, preparing rare earth metal-molybdenum binary infiltration layer: rare earth metals are used as permeation activators in a permeation coating system, and lanthanum (La), cerium (Ce), neodymium (Nd) or samarium (Sm) are respectively selected. The invention takes rare earth La as an example to examine the influence of La elements with different contents on the comprehensive performance of the diffusion coating. Wherein the selected range of La element content is 3.0%.
Thirdly, forming a uniform and compact rare earth metal-molybdenum binary infiltration layer on the surface of the kovar alloy by adopting a supersonic plasma spraying technology: the supersonic plasma spraying process is characterized in that propane and compressed air are used as plasma forming gas, and the ratio of the compressed air amount to the propane amount is 5:1. The spraying current is 350A; the air pressure is 0.6MPa; the spraying distance was 230mm.
And step four, testing the thickness and the binding force of the infiltration layer. The experiment tests the bonding strength between the coating and the substrate according to the scratch method: the bonding strength of the infiltration layer and the kovar alloy matrix is measured by a scratch method, the thickness of the coating is 9 mu m, the bonding property with the matrix is good, and the microhardness is 2800HV0.3.
Example 4:
the specific process of the preparation method for the rare earth metal-molybdenum binary infiltration layer on the surface of the kovar alloy is the same as that of the embodiment 1, and specific technological parameter conditions are shown in the table 1, except that the alloy type selected in the embodiment is stainless steel (chrome-containing alloy steel) suitable for glass sealing.
Example 5:
the specific process is the same as that of example 1, and specific technological parameter conditions are shown in Table 1, except that the alloy types selected in the example are copper and copper alloy (brass and bronze) suitable for glass sealing.
Example 6:
the specific process is the same as that of example 1, and specific technological parameter conditions are shown in Table 1, except that the alloy type selected in the example is iron-nickel alloy suitable for glass sealing.
Example 7:
the specific process is the same as that of example 1, and specific technological parameter conditions are shown in Table 1, except that the alloy type selected in the example is Fe-Ni-Cr alloy suitable for glass sealing.
The optimal technological parameter combination is as follows: rare earth metal is used as a permeation activating agent in a permeation coating system, and the content of La element is 2.0 percent; the spraying current 310A and the air pressure were 0.5MPa, and the spraying distance was 200mm. The binary infiltration layer obtained under the spraying parameters is compact and uniform, the porosity is small, the bonding strength of the infiltration layer and the kovar alloy matrix is measured by adopting a scratch method, the thickness of the coating is 10 mu m, the bonding property with the matrix is good, and the microhardness is 3000HV0.4.
Table 1 formulation composition of each example
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (6)
1. The preparation method of the rare earth metal-molybdenum binary infiltration layer for the surface of the kovar alloy is characterized by comprising the following steps of:
step one, preprocessing a kovar alloy matrix: thoroughly removing greasy dirt, residues and oxide films on the surface of a matrix to obtain a clean active surface, and placing the kovar alloy matrix in alcohol for ultrasonic cleaning for 15min to remove surface grease; treating the surface of the kovar alloy matrix by using a sand blasting machine, and performing sand blasting coarsening treatment by using 46# brown corundum, wherein the sand blasting pressure is 0.4MPa; taking out, washing with deionized water and alcohol, and drying to obtain a kovar alloy matrix;
step two, preparing rare earth metal-molybdenum binary infiltration layer: rare earth metal is used as a permeation activator in a permeation coating system, lanthanum (La), cerium (Ce), neodymium (Nd) or samarium (Sm) is respectively selected, molybdenum powder particles improve the dispersion capacity of the permeation coating system, and the preferred orientation and texture coefficient of crystal faces of the kovar alloy permeation coating are changed, so that the coating crystal grains are thinned, and a uniform and compact coating is obtained;
thirdly, forming a uniform and compact rare earth metal-molybdenum binary infiltration layer on the surface of the kovar alloy by adopting a supersonic plasma spraying process;
and step four, testing the thickness and the binding force of the infiltration layer.
2. The method for preparing the rare earth metal-molybdenum binary infiltration layer for the surface of the kovar alloy, as claimed in claim 1, is characterized in that the components of the spraying powder are rare earth metal and Mo powder, the spraying powder is prepared by adopting a spray granulation method, the rare earth metal and Mo powder are mixed for 2 hours in a mixer, and the spraying powder is obtained after drying, and the powder is spherical or nearly spherical, has an average particle size of 10-40 mu m and forms better fluidity in the spraying process.
3. The method for preparing rare earth metal-molybdenum binary infiltration layer for kovar alloy surface according to claim 2, characterized in that the supersonic plasma spraying process is selected to be that propane+compressed air is used as plasma forming gas, in the spraying process, the compressed air amount and the propane amount are in a fixed ratio of 5:1, and the spraying current is 270-350A; the air pressure is 0.4-0.6 MPa; the spraying distance is 170-230 mm.
4. The method for preparing rare earth metal-molybdenum binary infiltration layer for kovar alloy surface according to claim 3, wherein the bonding strength of infiltration layer and kovar alloy substrate is measured by scratch method, the thickness of the coating is 10 μm, the bonding property with the substrate is good, and the microhardness is 3000HV0.4.
5. The method for preparing rare earth metal-molybdenum binary infiltration layer for kovar alloy surface according to claim 4, wherein the kovar alloy substrate is made of 4J29, and is suitable for stainless steel, copper alloy, iron-nickel alloy and iron-nickel-chromium alloy systems for glass sealing.
6. The method for preparing rare earth metal-molybdenum binary plating for kovar surfaces according to claim 5, characterized in that the stainless steel is a chrome-containing alloy steel, and the copper alloy is brass or bronze.
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